【作者】 吴丹；

【导师】 马秀玲； 项生昌；

【作者基本信息】 福建师范大学 ， 分析化学， 2017， 硕士

【摘要】 基于金属有机框架(MOFs)的热解衍生物,因其结构均匀且化学性质稳定,近几年引起了广泛关注,在电化学传感和燃料电池等领域展现了良好的应用前景。本论文以结构可控的MOFs为模板,通过热处理成功制备了几种不同的衍生物,利用多种表征手段对它们的结构进行了探究;同时探讨了其作为传感器对环境污染物水合肼、对苯二酚和邻苯二酚两种异构体的电化学检测,以及作为氧还原反应(ORR)电极材料的电化学性质。首先,利用溶剂热法合成了 HKUST-1,以其为前驱体衍生得到CuO纳米材料,并将该纳米材料修饰玻碳电极,应用于水环境中高毒性污染物水合肼的电化学检测。结果表明,该传感器在1.98-169.3 μM和232-2096 μM范围内,其响应电流与水合肼浓度呈现出良好的线性关系,且其检测限较低,为0.075 μM(S/N=3)。实验构建的传感器还表现出较好的选择性,且对实际水样的测定也取得了令人满意的结果。该方法为水合肼的快速测定提供了参考。其次,选用了两例同构的三维框架型MOFs(FJU-40-H和FJU-40-NH2),衍生得到两种多孔碳材料:NPC-FJU-40-H和NPC-FJU-40-NH2,并以此分别构建了同时检测对苯二酚(HQ)和邻苯二酚(CT)的电化学传感器。实验发现,HQ和CT在NPC-FJU-40-H/GCE上能很好的区分响应,而在NPC-FJU-40-NH2/GCE上则无明显响应。HQ和CT在NPC-FJU-40-H/GCE上的线性范围分别为1-70 μM和1-100 μM,检测限分别为0.18 μM和0.31 μM,其线性范围较宽,检测限较低。实验结果说明:配体官能团的差异性可导致衍生后的多孔碳材料性能的差异,为高性能传感器的构建提供另一思路。最后,基于化合物FJU-40-H(a)和FJU-40-NH2(b),采用异质外延法进一步合成核壳型结构化合物b@a和a@b,并分别以a、b、b@a和a@b为模板衍生得到氮掺杂的多孔碳材料:NPC-a-4h、NPC-b-4h、NPC-b@a-4h、NPC-a@b-4h,对它们的ORR催化性能进行了研究。氧还原催化效果NPC-a@b-4h>NPC-b@a-4h>NPC-a-4h>NPC-b-4h,NPC-a@b-4h表现出更正的氧还原电位(-0.203V)和初始电位(-0.068V)。结果表明,核壳结构的引入提升了氧还原催化性能。更多还原

【Abstract】 Due to the uniform structure and stable chemical properties,the pyrolysis derivatives based on metal-organic frameworks have attracted considerable attention in recent years,they have a good application prospect in the fields of electrochemical sensing and fuel cell.In this paper,several kinds of derivatives were successfully prepared by heating treatment,which used MOFs with controllable structure as templates,and their structures were investigated by means of various characterization.At the same time,the prepared materials were used as the sensors to electrochemical detection hydrazine hydrate and common phenolic pollutants(hydroquinone and catechol)in environment,and as the electrode materials for oxygen reduction reaction.Firstly,HKUST-1 was synthesized by solvothermal method,and used it as the precursor to obtain CuO nanomaterial,then modified it on the glassy carbon electrode,and applied to electrochemical detect hydrazine hydrate,which is a kind of highly toxic pollutants in water environment.The results showed that the response current had a good linear relationship with the hydrazine hydrate concentration in the range of 1.98-169.3μM and 232-2096 μM,and the detection limit was low,which was 0.075 μM(S/N = 3).The constructed sensor also showed better selectivity,and the detection results of actual water samples were also satisfactory.The method provided a reference for the rapid determination of hydrazine hydrate.Secondly,two isostructural MOFs(FJU-40-H and FJU-40-NH2)were selected to obtain two kinds of porous carbon materials:NPC-FJU-40-H and NPC-FJU-40-NH2,and the electrochemical sensors for simultaneous detection catechol and hydroquinone were constructed.The experiment showed that HQ and CT had a good response on NPC-FJU-40-H/GCE,but had no obvious response on NPC-FJU-40-NH2/GCE.The linear range of HQ and CT on NPC-FJU-40-H/GCE were 1-70 μM and 1-100 μM respectively,and the detection limits were 0.18 μM and 0.31 μM respectively,the linear range was wider and the detection limit was low.The results revealed that the differences in ligand functional groups could lead to different performances of the derived porous carbon material,which provided another way for the construction of high-performance sensors.Finally,based on compound FJU-40-H(a)and compound FJU-40-NH2(b),two core-shell structural compounds were synthesized by hetero-epitaxy,compound b@a and compound a@b.Then used a,b,b@a,a@b as templates to obtain four nitrogen-doped porous carbon materials:NPC-a-4h,NPC-b-4h,NPC-b@a-4h and NPC-a@b-4h.Their catalytic properties of oxygen reduction were also studied.The oxygen reduction catalytic results was that NPC-a@b-4h>NPC-b@a-4h>NPC-a-4h>NPC-b-4h,NPC-a@b-4h exhibited a more positive oxygen reduction potential(-0.203 V)and onset potential(-0.068 V).The results showed that the introduction of core-shell structure could promot the catalytic performance of oxygen reduction.更多还原